CN103575729A - Time-temperature synthesizer containing intelligent switch - Google Patents

Abstract

The invention discloses a time-temperature synthesizer containing an intelligent switch, comprising: a base layer; a reaction layer attached to the base layer; an activator for activating the reaction layer; wherein, the base layer is composed of The composition is composed of transparent insulating material; the reaction layer is a conductive polymer film; the activator is an electrolyte solution. The time-temperature synthesizer with intelligent switch prepared by the present invention has simple structure, simple preparation process and low cost. The change in conductivity of the electrolyte after doping turns off the RFID transponder.

Description

A Time-Temperature Synthesizer with Intelligent Switch

technical field

The invention relates to the field of time-temperature indication, in particular to a time-temperature synthesizer with an intelligent switch based on electrochemical reaction.

Background technique

Time-temperature indicator (Time-Temperature Indicator, TTI) is a simple device that is easy to measure or observe and is related to time and temperature changes. Its changes reflect the temperature of the whole or part of the food, and can indicate the monitored food. The temperature change process experienced, and then it is possible to estimate the deterioration range and remaining shelf life of food according to the temperature change process. Its reaction principle includes irreversible changes in mechanical, chemical, electrochemical, enzymatic reactions, microorganisms, etc. This change is related to temperature and is continuously accumulated. The result of the change is usually in the form of visible physical and chemical phenomena such as color Changes are reflected. The TTI device was proposed more than 40 years ago and has been applied to biological product vaccines that need to be refrigerated. Its application in food began at the end of the last century, mainly for those refrigerated and frozen foods that are sensitive to temperature, such as fresh milk, Frozen fish, meat, seafood products, etc. At present, there are three main types of TTI commercially used in the world: the first type is 3M Monitor Mark of 3M Company, which is a kind of TTI using the principle of diffusion, relying on the color interface movement of the colored chemical substances in the process of diffusion and migration , that is, the diffusion distance of the colored fatty acid ester on the porous paper core with excellent water absorption is used as the response value to record the change of temperature with time. When the storage temperature is lower than the melting point of the ester, the indicator does not respond; when the storage temperature is high When the melting point of the ester is reached, the indicator begins to respond. The applicable temperature range of the diffusion indicator is related to the type of ester selected; the second type is Vistab Check Point from VITSAB. The principle of this TTI is based on a The enzymatic hydrolysis of a lipid substrate under controlled conditions reduces the pH and causes the color of the acid-base indicator to change. The higher the temperature, the faster the protons released by the enzyme-catalyzed hydrolysis of the lipid substrate, and its color changes. The third category is the Fresh Check of LifeLines Technology, whose principle is chemical polymerization to form colored polymers, specifically through the solid-state polymerization of colorless alkyne monomers The temperature change is recorded by the color change after the formation of an opaque colored polymer. The polymerization reaction accelerates as the temperature increases, resulting in a faster darkening of the indicator color. The time-temperature indicator must be frozen before use. so as not to activate the reaction.

Time-temperature indicator (TTI) reminds consumers of the possible temperature changes of products through visual changes, thus providing an important way for consumers to judge food quality and choose safer food. At present, besides food, the application field of TTI has also begun to show its strength in other fields such as pharmaceutical products (vaccine, serum), tobacco, cosmetics and electronic products.

However, the existing TTI can usually only track and record the time and temperature changes of the indicated product, and display the cumulative effect of time and temperature through color changes, and other functions have not been reported yet.

Contents of the invention

The purpose of the present invention is to solve the technical problems existing in the existing time-temperature indicator, and provide a new type of time-temperature synthesizer with intelligent switch, which can not only track and record the time and temperature changes, but also use the time-temperature comprehensive The change in the conductivity of the conductive polymer and electrolyte doped in the device turns off the RFID transponder in the closed loop.

In order to realize the purpose of the present invention, the present invention provides a kind of time-temperature synthesizer containing intelligent switch on the one hand, comprising:

basal layer;

a reactive layer attached to the base layer;

An activator for activating the reaction layer; wherein,

The base layer is composed of a transparent insulating material;

The reaction layer is a conductive polymer film;

The activator is an electrolyte solution.

Wherein, the transparent insulating material is selected from transparent plastic.

In particular, said transparent plastic is selected from polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) plastics or polycarbonate (PC) plastic, preferably PET.

Wherein, the conductive polymer is doped polyaniline, polypyrrole or PEDOT:PSS, preferably doped polyaniline.

In particular, the doped polyaniline is polyaniline doped with acid.

Wherein, the acid is an organic acid or an inorganic acid.

In particular, the inorganic acid is hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, etc.; the organic acid is citric acid, benzenesulfonic acid or dodecylbenzenesulfonic acid, etc.

Wherein, the polypyrrole is a doped polypyrrole; the PEDOT:PSS refers to a polymer polymer formed by PEDOT (poly-(3,4-ethylenedi-oxythiophene)) doped with PSS (poly(tyrenesulfonate)) thing.

In particular, the doped polypyrrole is a polypyrrole doped with anions.

In particular, the anions are selected from Cl ⁻ , benzenesulfonate and anionic surfactants.

Wherein, the electrolyte solution is an alkaline electrolyte solution.

In particular, the alkaline electrolyte solution is selected from NaOH solution, KOH solution, Ca(OH) ₂ solution, ammonia water, etc., preferably NaOH solution.

In particular, the concentration of the NaOH solution is 0.001-1 mol/L, preferably 0.1 mol/L.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the conductive polymer film, a time indicating region that characterizes the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, two electrodes are formed on the switch area.

Wherein, the lower surface of the base layer has a time scale representing time.

In particular, the reaction layer is bounded by the time scale on the lower surface of the base layer, the reaction layer inside the time scale is the time indicator area, and the reaction layer outside the time scale is the switch area.

Wherein, the two electrodes on the switch area are formed by cutting.

In particular, the electrodes are generally rectangular in shape.

In particular, it also includes a migration layer attached to the reaction layer, and the migration layer is a hydrophilic polymer film.

Wherein, the hydrophilic polymer is selected from one or more of polyvinyl alcohol, hydroxyethyl cellulose, branched starch and chitosan.

Another aspect of the present invention provides a method for preparing a time-temperature synthesizer containing an intelligent switch, wherein the time-temperature synthesizer includes:

basal layer;

a reactive layer attached to the base layer;

An activator for activating the reaction layer; wherein,

The base layer is composed of a transparent insulating material;

The reaction layer is a conductive polymer film;

The activator is an electrolyte solution, and the method comprises the steps of:

A) coating the conductive polymer solution on the upper surface of the base layer, and then performing drying treatment to obtain the reaction layer;

B) When using the time-temperature synthesizer, the activator is dropped into the front end of the reaction layer.

Wherein, the conductive polymer solution described in step A) is an aqueous solution of polyaniline, and its weight percent concentration is 5-10%.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the conductive polymer film, a time indicating region that characterizes the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, two electrodes are formed on the switch area.

In particular, it also includes printing a time scale representing time on the lower surface of the base layer, wherein the corresponding reaction layer within the time scale is a time indication area representing the time length of the chemical doping reaction;

The reaction layer outside the time scale is the switching area.

Wherein, the formation method of the two electrodes of the switch region of the reaction layer is as follows:

Open a gap in the switch area of the reaction layer along the direction perpendicular to the length of the reaction layer, and the switch areas on both sides of the gap are two electrodes; or

Along the direction perpendicular to the width of the reaction layer, a gap is opened in the switch region of the reaction layer, and the switch regions on both sides of the gap are two electrodes, or

Along the direction perpendicular to the length of the reaction layer, two protrusions extend outward from the switch area of the reaction layer, and the two protrusions are two electrodes.

Wherein, it also includes coating the hydrophilic polymer solution on the upper surface of the reaction layer, and then performing drying treatment to obtain the migration layer.

In particular, the hydrophilic polymer solution is an aqueous solution of polyvinyl alcohol, and its weight percent concentration is 5-20%.

The present invention has the following advantages:

1. The time-temperature synthesizer containing intelligent switch prepared by the present invention can not only track and record time and temperature changes, but also use the change of conductivity after the conductive polymer and electrolyte doping in the time and temperature synthesizer to control the closed loop The RFID transponder in the switch is turned off.

2. The time-temperature synthesizer with intelligent switch prepared by the present invention has simple structure, simple preparation process and low cost.

3. The time-temperature synthesizer with intelligent switch prepared by the present invention can close the RFID transponder at a specific time, which expands the application range of RFID.

Description of drawings

Fig. 1 is the front schematic view of the time-temperature synthesizer containing intelligent switch prepared in embodiment 1;

Fig. 2 is the time-temperature synthesizer containing intelligent switch of Fig. 1 along the sectional schematic diagram of A-A line;

Fig. 3 is the front schematic view of the time-temperature synthesizer containing intelligent switch prepared in embodiment 2;

Fig. 4 is the time-temperature synthesizer containing intelligent switch of Fig. 3 along B-B line sectional schematic diagram;

Fig. 5 is the sectional schematic diagram along C-C line of the time-temperature synthesizer containing intelligent switch of Fig. 3;

Fig. 6 is the front schematic view of the time-temperature synthesizer containing intelligent switch prepared in embodiment 3;

Fig. 7 is a schematic sectional view of the time-temperature synthesizer containing the intelligent switch of Fig. 6 along the D-D line;

Fig. 8 is the front schematic view of the time-temperature synthesizer containing intelligent switch prepared in embodiment 4;

Fig. 9 is a schematic cross-sectional view along the E-E line of the time-temperature synthesizer containing the intelligent switch of Fig. 8;

Fig. 10 is a schematic cross-sectional view along the F-F line of the time-temperature synthesizer containing the intelligent switch of Fig. 8;

Fig. 11 is the front schematic view of the time-temperature synthesizer containing intelligent switch prepared in embodiment 5;

Fig. 12 is a schematic cross-sectional view along the G-G line of the time-temperature synthesizer containing the intelligent switch of Fig. 11;

Fig. 13 is the combination of the time-temperature synthesizer containing the intelligent switch and the RFID transponder prepared in Example 1

The schematic diagram used;

Fig. 14 is a schematic diagram of the time-temperature synthesizer containing the intelligent switch prepared in Example 1 after the RFID transponder is turned off.

Reference signs: 1. Time-temperature synthesizer with intelligent switch; 2. Activator; 3. Gap; 4. Time scale; 5. RFID transponder; 11 base layer; 12. reaction layer; 13. migration layer; 14. First electrode; 15. Second electrode; 20. Interface; 41. Starting point of time scale; 42. End point of time scale; 51. Antenna coil; 52. Chip.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, and the advantages and characteristics of the present invention will become clearer along with the description. However, these embodiments are only exemplary and do not constitute any limitation to the scope of the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the protection scope of the present invention.

Example 1

(1) Time-temperature synthesizer with smart switch

As shown in Figures 1 and 2, the time-temperature synthesizer 1 with an intelligent switch includes:

base layer 11;

a reaction layer 12 attached to the upper surface of the base layer;

a time scale 4 representing time located on the lower surface of the base layer;

Activator 2 for activating the reactive layer.

Wherein, the base layer is selected from polyethylene terephthalate (PET), other plastics such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) or polycarbonate Polyester (PC) plastics are suitable for use in the present invention.

The reaction layer is a doped polyaniline (PANI: DBSA (dodecylbenzene sulfonic acid)) film, other conductive polymers such as polypyrrole, polystyrene sulfonic acid doped poly 3,4-ethylene bismuth Oxythiophene (PEDOT:PSS) is suitable for use in the present invention.

The dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) of the present embodiment selects the PANI:DBSA that the percentage by weight concentration is 10%, other such as the PANI:DBSA that the percentage by weight concentration is 5-10% all applicable in the present invention.

The activator is 0.1mol/L NaOH solution, and other alkaline electrolyte solutions such as KOH, Ca(OH) ₂ , and ammonia water are all suitable for the present invention.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the reaction layer, a time indication area representing the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, the time scale starting point 41 is located at one end of the base layer along the length direction and corresponds to one end of the reaction layer. One end of the reaction layer corresponding to the time scale starting point 41 is the top of the reaction layer, and the other end of the reaction layer corresponding to the time scale end point 42 is the end of the reaction layer, and the length of the time scale is shorter than the length of the reaction layer, i.e. the reaction layer 12 The end is located outside the end point 42 of the time scale;

Among them, the reaction layer within the time scale 4 is the time indicator area; the reaction layer outside the time scale 4 is the switch area;

In the direction perpendicular to the length of the base layer, a gap 3 is opened in the switch area of the reaction layer, and the gap divides the switch area into two parts, namely electrodes 14 and 15 . Wherein the first electrode 14 is the switch area corresponding to the end point 42 of the gap and the time scale; the second electrode 15 is the switch area outside the gap.

The notch 3 in the embodiment of the present invention is rectangular as a whole, and its length is less than the width of the reaction layer, that is, the length extending along the width direction of the reaction layer is less than the width of the reaction layer; its width is 2-4mm, that is, along the length direction of the base layer The distance is 2-4mm; its depth is the same as the thickness of the reaction layer.

The gap can be in any shape, as long as the reaction layer in the switch area is divided into two parts.

The base layer 11 and the reaction layer 12 are cuboid, the base layer 11 has a length of 10-50 mm, a width of 2-10 mm, and a thickness of 0.01-0.02 mm; the length of the reaction layer 12 is 10-50 mm, and a thickness of 0.001-0.005 mm , width 2-10mm.

In the embodiment of the present invention, the length of the base layer 11 is selected to be 15 mm, the width is 5 mm, and the thickness is 0.02 mm; the length of the reaction layer 12 is 15 mm, the thickness is 0.001 mm, and the width is 5 mm.

(2) Preparation method of time-temperature synthesizer with intelligent switch

1) Use a spin coater (Shenyang Sile Company) to coat a polyaniline solution (PANI:DBSA) doped with dodecylbenzenesulfonic acid with a concentration of 10% by weight on polyterephthalene by spin coating. The upper surface of the ethylene glycol formate (PET) base layer 11, and then put the PET base layer coated with the PANI:DBSA solution into a dryer (relative humidity less than 20%, temperature 15-30°C) to dry for 12-24 hour, PANI:DBSA forms one deck green PANI:DBSA conductive polymer dry film on the PET base layer, promptly makes reaction layer 12, makes the thickness of reaction layer be 1 ± 0.2 μ m;

2) Cut the PET base material coated with the reaction layer 12 into a sample of 15 (length)×5 (width) mm;

3) According to the doping diffusion speed of the activator (0.1mol/L NaOH solution) on the reaction layer, print the time scale 4 representing the time on the lower surface of the base layer, as the reference shelf life of the product to be indicated, with the base layer along One end of the longitudinal direction is used as the starting point 41 of the time scale 4, and the starting position corresponds to the top of the reaction layer 12; the other end near the base layer is used as the end point 42 of the time scale 4, and the end point is located near the end of the reaction layer 12, and the reaction layer The length of is longer than the length of the time scale. The reaction layer within the time scale is used as the time indicator area; the reaction layer outside the time scale is used as the switch area;

4) In the switch area of the reaction layer, perpendicular to the length direction of the base layer, a rectangular gap 3 is cut on the side wall of the reaction layer along the length direction with a blade, and the switch area on both sides of the gap 3 forms two electrodes, where the time The reaction layer between the switching area corresponding to the end point 42 of the scale and the gap is the first electrode 14, and the switching area outside the gap is the second electrode 15;

5) When in use, drop the activator into the front end of the time indication area of the reaction layer, that is, on the reaction layer corresponding to the starting point 41 of the time scale.

Example 2

(1) Time-temperature synthesizer with smart switch

As shown in Figure 3-5, the time-temperature synthesizer 1 with intelligent switch includes:

base layer 11;

a reaction layer 12 attached to the upper surface of the base layer;

a time scale 4 representing time located on the lower surface of the base layer;

Activator 2 for activating the reactive layer.

Wherein, the base layer is selected from polyethylene terephthalate (PET), other plastics such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) or polycarbonate Polyester (PC) plastics are suitable for use in the present invention.

The reaction layer is a doped polyaniline (PANI: DBSA (dodecylbenzene sulfonic acid)) film, other conductive polymers such as polypyrrole, polystyrene sulfonic acid doped poly 3,4-ethylene bismuth Oxythiophene (PEDOT:PSS) is suitable for use in the present invention.

The dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) of the present embodiment selects the PANI:DBSA that the weight percent concentration is 5%, and other such as the weight percent concentration that is 5-10% PANI:DBSA is applicable in the present invention.

The activator is 0.1mol/L NaOH solution, and other alkaline electrolyte solutions such as KOH, Ca(OH) ₂ , and ammonia water are all suitable for the present invention.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the reaction layer, a time indication area representing the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, the time scale starting point 41 is located at one end of the base layer along the length direction and corresponds to one end of the reaction layer. One end of the reaction layer corresponding to the time scale starting point 41 is the top of the reaction layer, and the other end of the reaction layer corresponding to the time scale end point 42 is the end of the reaction layer, and the length of the time scale is shorter than the length of the reaction layer, i.e. the reaction layer 12 The end is located outside the end point 42 of the time scale;

Among them, the reaction layer within the time scale 4 is the time indicator area; the reaction layer outside the time scale 4 is the switch area;

In the direction perpendicular to the width of the base layer, a gap 3 is opened in the switch area of the reaction layer, and the gap divides the switch area into two parts, namely electrodes 14 and 15 . The switching area above the notch is the first electrode 14 ; the switching area below the notch is the second electrode 15 .

The gap 3 in the embodiment of the present invention is generally rectangular, and its width is smaller than the width of the reaction layer, that is, the length extending along the width direction of the reaction layer is less than the width of the reaction layer, and its width is 1-4mm, that is, along the width direction of the base layer The distance is 1-4mm, the depth is equal to the thickness of the reaction layer, and the length is equal to the length of the switch area.

The gap can be in any shape, as long as the reaction layer 12 of the switch region is divided into two parts separated from each other along the width direction of the reaction layer.

(2) Preparation method of time-temperature synthesizer with intelligent switch

1) In addition to selecting dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) with a concentration of 5% by weight, coating dodecylbenzenesulfonic acid-doped polyaniline solution on the base layer (PET film) Mixed polyaniline solution (PANI:DBSA) the step that makes reaction layer is identical with embodiment 1;

2) Cut the PET base material coated with the reaction layer 12 into a sample of 15 (length)×5 (width) mm;

3) According to the doping diffusion speed of the activator (0.1mol/L NaOH solution) on the reaction layer, print the time scale 4 representing the time on the lower surface of the base layer, as the reference shelf life of the product to be indicated, with the base layer along One end of the longitudinal direction is used as the starting point 41 of the time scale 4, and the starting position corresponds to the top of the reaction layer 12; the other end near the base layer is used as the end point 42 of the time scale 4, and the end point is located near the end of the reaction layer 12, and the reaction layer The length of is longer than the length of the time scale. The reaction layer within the time scale is used as the time indicator area; the reaction layer outside the time scale is used as the switch area;

4) In the switch area of the reaction layer, perpendicular to the width direction of the base layer, a rectangular gap 3 is cut on the side wall of the reaction layer along the width direction with a blade, and the switch area on both sides of the gap 3 forms two electrodes, of which The switch region reaction layer above the notch 3 is the first electrode 14, and the switch region reaction layer below the notch 3 is the second electrode 15;

5) When in use, drop the activator into the front end of the time indicating area where the activator is dropped into the reaction layer, that is, the reaction layer corresponding to the starting point 41 of the time scale.

Example 3

(1) Time-temperature synthesizer with smart switch

As shown in Figures 6 and 7, the time-temperature synthesizer 1 with an intelligent switch includes:

base layer 11;

a reaction layer 12 attached to the upper surface of the base layer;

a time scale 4 representing time located on the lower surface of the base layer;

Activator 2 for activating the reactive layer.

Wherein, the base layer is selected from polyethylene terephthalate (PET), other plastics such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) or polycarbonate Polyester (PC) plastics are suitable for use in the present invention.

The reaction layer is a doped polyaniline (PANI: DBSA (dodecylbenzene sulfonic acid)) film, other conductive polymers such as polypyrrole, polystyrene sulfonic acid doped poly 3,4-ethylene bismuth Oxythiophene (PEDOT:PSS) is suitable for use in the present invention.

The dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) of the present embodiment selects the PANI:DBSA that the weight percentage concentration is 7%, other such as the weight percent concentration that is 5-10% PANI:DBSA all applicable in the present invention.

The activator is 0.1mol/L NaOH solution, and other alkaline electrolyte solutions such as KOH, Ca(OH) ₂ , and ammonia water are all suitable for the present invention.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the reaction layer, a time indication area representing the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, the time scale starting point 41 is located at one end of the base layer along the length direction and corresponds to one end of the reaction layer. One end of the reaction layer corresponding to the time scale starting point 41 is the top of the reaction layer, and the other end of the reaction layer corresponding to the time scale end point 42 is the end of the reaction layer, and the length of the time scale is shorter than the length of the reaction layer, i.e. the reaction layer 12 The end is located outside the end point 42 of the time scale;

Among them, the reaction layer within the time scale 4 is the time indicator area; the reaction layer outside the time scale 4 is the switch area;

In a direction perpendicular to the length of the base layer, the switch region of the reaction layer extends outward to form two protrusions, which are electrodes 14 and 15 . The protrusion corresponding to the end point 42 of the time scale is the first electrode 14; the other protrusion is the second electrode 15, and the distance between the two electrodes is 1-4 mm.

(2) Preparation method of time-temperature synthesizer with intelligent switch

1) In addition to selecting dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) with a concentration of 7% by weight, coating dodecylbenzenesulfonic acid-doped polyaniline solution on the base layer (PET film) Mixed polyaniline solution (PANI:DBSA) the step that makes reaction layer is identical with embodiment 1;

2) According to the doping diffusion speed of the activator (0.1mol/L NaOH solution) on the reaction layer, print the time scale 4 representing the time on the lower surface of the base layer, as the reference shelf life of the product to be indicated, with the base layer along One end of the longitudinal direction is used as the starting point 41 of the time scale 4, and the starting position corresponds to the top of the reaction layer 12; the other end near the base layer is used as the end point 42 of the time scale 4, and the end point is located near the end of the reaction layer 12, and the reaction layer The length of is longer than the length of the time scale. The reaction layer within the time scale is used as the time indicator area; the reaction layer outside the time scale is used as the switch area;

3) Cut the PET base material coated with the reaction layer 12 into a cuboid sample with two parallel protrusions in the switch area, the two protrusions are two electrodes, and the first electrode corresponds to the end point 42 of the time scale The corresponding parts of the base layer and the reaction layer extend outwards, and the second electrode is formed by extending the corresponding parts of the base layer and the reaction layer between the first electrode and the other end of the switch area. The two electrodes and the length of the cuboid The direction of the electrode is vertical, and the distance between the two electrodes is 3mm;

4) When in use, drop the activator into the front end of the time indication area of the reaction layer, that is, on the reaction layer corresponding to the starting point 41 of the time scale.

Example 4

(1) Time-temperature synthesizer with smart switch

As shown in Figure 8-10, the time-temperature synthesizer 1 with intelligent switch includes:

base layer 11;

a reaction layer 12 attached to the upper surface of the base layer;

A migration layer 13 attached to the upper surface of the reaction layer;

a time scale 4 representing time located on the lower surface of the base layer;

Activator 2 for activating the reactive layer.

Wherein, the base layer is selected from polyethylene terephthalate (PET), other plastics such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) or polycarbonate Polyester (PC) plastics are suitable for use in the present invention.

The reaction layer is a doped polyaniline (PANI: DBSA (dodecylbenzene sulfonic acid)) film, other conductive polymers such as polypyrrole, polystyrene sulfonic acid doped poly 3,4-ethylene bismuth Oxythiophene (PEDOT:PSS) is suitable for use in the present invention.

The dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) of the present embodiment selects the PANI:DBSA that the percentage by weight concentration is 10%, other such as the PANI:DBSA that the percentage by weight concentration is 5-10% all applicable in the present invention.

The activator is 0.1mol/L NaOH solution, and other alkaline electrolyte solutions such as KOH, Ca(OH) ₂ , and ammonia water are all suitable for the present invention.

Polyvinyl alcohol (PVA) is selected as the migration layer, and other hydrophilic polymers such as hydroxyethyl cellulose, branched starch, and chitosan are all suitable for the present invention.

The polyvinyl alcohol solution in the migration layer in this embodiment is selected to have a weight percentage concentration of 5% polyvinyl alcohol solution, and other polyvinyl alcohol solutions such as a weight percentage concentration of 5-20% are suitable for the present invention.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the reaction layer, a time indication area representing the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, the time scale starting point 41 is located at one end of the base layer along the length direction and corresponds to one end of the reaction layer. One end of the reaction layer corresponding to the time scale starting point 41 is the top of the reaction layer, and the other end of the reaction layer corresponding to the time scale end point 42 is the end of the reaction layer, and the length of the time scale is shorter than the length of the reaction layer, i.e. the reaction layer 12 The end is located outside the end point 42 of the time scale;

Among them, the reaction layer within the time scale 4 is the time indicator area; the reaction layer outside the time scale 4 is the switch area;

The migration layer 13 is closely attached to the upper surface of the reaction layer, and the length of the migration layer is the same as the length of the time scale, and one end along the length direction of the base layer corresponds to the starting point of the time scale, and the other end corresponds to the end point of the time scale; its width smaller than the width of the reaction layer, and its two ends along the width direction of the base layer are located within the two ends of the reaction layer along the width direction of the base layer.

In the direction perpendicular to the width of the base layer, a gap 3 is opened in the switch area of the reaction layer, and the gap divides the switch area into two parts, namely electrodes 14 and 15 . The switching area above the notch is the first electrode 14 ; the switching area below the notch is the second electrode 15 .

(2) Preparation method of time-temperature synthesizer with intelligent switch

1) Coating dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) on the base layer (PET film) to prepare the reaction layer is the same as in Example 1;

2) Cut the PET base material coated with the reaction layer 12 into a sample of 30 (length)×15 (width) mm;

3) Perpendicular to the width direction of the base layer, use a blade to cut a rectangular gap 3 on the side wall of the reaction layer along the width direction. The switch area on both sides of the gap 3 forms two electrodes, and the switch area above the gap 3 reacts layer is the first electrode 14, and the reaction layer in the switch region below the gap 3 is the second electrode 15;

4) Along the length direction of the base layer, paste 2 tapes of 30cm (length) × 2.5cm (width) along the two electrodes in the length direction of the reaction layer, the distance between the two tapes is 10mm, and then use a spin coater Be that the polyvinyl alcohol solution of 5% by weight percentage concentration is coated on the reaction layer 12 that is pasted with protective tape in the mode of spin coating, put the PET base material that has been coated with polyvinyl alcohol solution into desiccator (relative humidity less than 20%, the temperature is 15-30°C) and dried for 12-24 hours, polyvinyl alcohol forms a layer of colorless polymer dry film on the reaction layer 12, that is, the migration layer 13, and the thickness of the migration layer 13 is 20± 0.2μm; and remove the protective tape;

5) According to the doping diffusion rate of the activator (0.1mol/L NaOH solution) that penetrates the migration layer on the reaction layer, print the time scale 4 representing the time on the lower surface of the base layer as the reference shelf life of the product to be indicated , the end point 42 of the time scale corresponds to the bottom of the gap, the starting point 41 of the time scale is located at one end away from the gap, the reaction layer inside the time scale is used as a time indicator area; the reaction layer outside the time scale is used as a switch area;

6) When in use, drop the activator onto the migration layer corresponding to the starting point 41 of the time scale.

Example 5

(1) Time-temperature synthesizer with smart switch

As shown in Figures 11 and 12, the time-temperature synthesizer 1 with an intelligent switch includes:

base layer 11;

a reaction layer 12 attached to the upper surface of the base layer;

A migration layer 13 attached to the upper surface of the reaction layer;

a time scale 4 representing time located on the lower surface of the base layer;

Activator 2 for activating the reactive layer.

Wherein, the base layer is selected from polyethylene terephthalate (PET), other plastics such as polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT) or polycarbonate Polyester (PC) plastics are suitable for use in the present invention.

The reaction layer is a doped polyaniline (PANI: DBSA (dodecylbenzene sulfonic acid)) film, other conductive polymers such as polypyrrole, polystyrene sulfonic acid doped poly 3,4-ethylene bismuth Oxythiophene (PEDOT:PSS) is suitable for use in the present invention.

The dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) of the present embodiment selects the PANI:DBSA that the percentage by weight concentration is 10%, other such as the PANI:DBSA that the percentage by weight concentration is 5-10% all applicable in the present invention.

The activator is 0.1mol/L NaOH solution, and other alkaline electrolyte solutions such as KOH, Ca(OH) ₂ , and ammonia water are all suitable for the present invention.

Polyvinyl alcohol (PVA) is selected as the migration layer, and other hydrophilic polymers such as hydroxyethyl cellulose, branched starch, and chitosan are all suitable for the present invention.

The polyvinyl alcohol solution in the migration layer in this embodiment is selected to have a concentration of 10% by weight, and other solutions such as polyvinyl alcohol with a concentration of 5-20% by weight are suitable for the present invention.

Wherein, the reaction layer includes:

During the chemical doping reaction between the activator and the conductive polymer in the reaction layer, a time indication area representing the time length of the chemical doping reaction;

a switch zone located at the end of said time indication zone;

Wherein, the time scale starting point 41 is located at one end of the base layer along the length direction and corresponds to one end of the reaction layer. One end of the reaction layer corresponding to the time scale starting point 41 is the top of the reaction layer, and the other end of the reaction layer corresponding to the time scale end point 42 is the end of the reaction layer, and the length of the time scale is shorter than the length of the reaction layer, i.e. the reaction layer 12 The end is located outside the end point 42 of the time scale;

Among them, the reaction layer within the time scale 4 is the time indicator area; the reaction layer outside the time scale 4 is the switch area;

The transfer layer 13 is closely attached to the upper surface of the reaction layer, and the transfer layer, the reaction layer and the base layer have the same shape and size;

In a direction perpendicular to the length of the base layer, the switch region of the reaction layer extends outward to form two protrusions, which are electrodes 14 and 15 . The protrusion corresponding to the end point 42 of the time scale is the first electrode 14 ; the other protrusion is the second electrode 15 .

(2) Preparation method of time-temperature synthesizer with intelligent switch

1) Coating dodecylbenzenesulfonic acid-doped polyaniline solution (PANI:DBSA) on the base layer (PET film) to prepare the reaction layer is the same as in Example 1;

2) Along the length direction of the base layer, cut the dried reaction layer and the base layer into a cuboid sample with two parallel and separated protrusions at one end of the reaction layer. The length of the cuboid is > 30mm, The width is 15 mm, the two protrusions are located on the side wall of the reaction layer along the length direction of the base layer, and the distance between the two is 5-20 mm, which is 5 mm in this embodiment;

3) Put a protective tape on the upper surface of the two protrusions, use a spin coater to coat a polyvinyl alcohol solution with a concentration of 10% by weight on the reaction layer with the protective tape, and then apply the polyethylene The PET base material of the alcohol solution is placed in a drier (relative humidity less than 20%, temperature 15-30°C) and dried for 12-24 hours, and the polyvinyl alcohol forms a layer of colorless polymer dry film on the reaction layer 12, The migration layer 13 is obtained, and the thickness of the migration layer 13 is 20±0.2 μm; the protective tape is removed, and the two exposed protrusions form two electrodes 14, 15;

4) According to the dopant diffusion rate of the activator (0.1mol/L NaOH solution) passing through the migration layer on the reaction layer, print the time scale 4 representing time on the lower surface of the base layer 11 as the product to be indicated The reference shelf life of , wherein, the end point 42 of the time scale corresponds to the first electrode, the second electrode is located outside the time scale, the starting point 41 of the time scale is located at the other end of the reaction layer away from the protruding part, according to the length of the time scale at the end away from the electrode Cut the base layer, reaction layer, and transfer layer to length. The reaction layer inside the time scale is the time indicator area, and the reaction layer outside the time scale is the switch area;

5) When in use, drop the activator onto the migration layer corresponding to the starting point 41 of the time scale.

Example 6

How to use the time-temperature synthesizer with smart switch:

1. Two electrodes 14,15 of the time-temperature synthesizer 1 containing the intelligent switch prepared in Example 1 are connected to the antenna coil 51 and the chip 52 of the RFID transponder 5, wherein the antenna coil 51 is connected to the first electrode, The chip 52 is connected to the second electrode 15 to form a closed loop;

2. Use a syringe to absorb the activator 2, that is, the NaOH solution with a concentration of 0.1mol/L, and then inject the NaOH solution into the reaction layer corresponding to the starting point 41 of the time scale of the time-temperature synthesizer to activate the time-temperature synthesizer, as shown in the figure 13.

The NaOH solution reacts with the green doped polyaniline in the reaction layer to generate blue non-conductive intrinsic polyaniline, as shown in formula (I):

(I)

A blue-green diffusion interface 20 is formed on the reaction layer, as shown in FIG. 13 .

As time goes on, the NaOH solution gradually diffuses from the starting point to the end point of the time scale, and the blue-green diffusion interface 20 moves along the reaction layer 12, so the distance moved by the blue-green diffusion interface 20 is linked with time , so as to intuitively reflect product quality and shelf life.

Before the time-temperature synthesizer 1 containing the smart switch is activated or before the blue-green interface 20 of the time-temperature synthesizer 1 diffuses to the end point 42 of the time scale (as shown in FIG. 13 ), the antenna coil of the RFID transponder The conductivity between the chip and the chip is 10.6-100 (s/cm), the circuit composed of the time-temperature indicator and the RFID transponder is in the on state, and the information on the chip of the RFID transponder can be read by the corresponding RFID The reader reads; after the time-temperature synthesizer containing the smart switch is activated, the electrolyte solution and the doped polyaniline in the reaction layer undergo a doping reaction to generate non-conductive intrinsic polyaniline. When the electrolyte solution diffuses to the time When the reaction layer corresponding to the end point of the scale reaches the position of the first electrode (as shown in Figure 14), the conductivity between the antenna coil of the RFID transponder and the chip is 0, the RFID transponder is turned off, and the information on the chip of the RFID transponder cannot Read by RFID reader.

Claims (10)

1. A time-temperature synthesizer containing an intelligent switch, characterized in that it comprises: Basal layer (11); a reactive layer (12) attached to said base layer; An activator (2) for activating the reactive layer; wherein, The base layer is composed of a transparent insulating material; The reaction layer is a conductive polymer film; The activator is an electrolyte solution. 2. The synthesizer of claim 1, wherein the reaction layer comprises: During the chemical doping reaction between the activator and the conductive polymer in the conductive polymer film, a time indicating region that characterizes the time length of the doping reaction; a switch zone located at the end of said time indication zone; Wherein, two electrodes are formed on the switch region. 3. The integrator according to claim 2, characterized in that it further comprises a migration layer (13) attached to the reaction layer (12), the migration layer being a hydrophilic polymer film. 4. The integrator according to claim 3, wherein the hydrophilic polymer is selected from one or more of polyvinyl alcohol, hydroxyethyl cellulose, amylopectin, and chitosan. 5. The synthesizer according to claim 1, wherein the conductive polymer is doped polyaniline. 6. The synthesizer of claim 1, wherein the conductive polymer is polypyrrole or PEDOT:PSS. 7. A preparation method of a time-temperature synthesizer containing an intelligent switch, wherein the time-temperature synthesizer comprises: Basal layer (11); a reactive layer (12) attached to said base layer; An activator (2) for activating the reactive layer; wherein, The base layer is composed of a transparent insulating material; The reaction layer is a conductive polymer film; The activator is an electrolyte solution; It is characterized in that the method comprises the steps of: 7-A) coating the conductive polymer solution on the upper surface of the base layer (11), and then performing drying treatment to obtain the reaction layer (12); 7-B) While using the time-temperature synthesizer, drop the activator (2) into the front end of the reaction layer. 8. The method according to claim 7, wherein the conductive polymer solution is a doped polyaniline aqueous solution, and its weight percent concentration is 5-10%. 9. The method according to claim 7, further comprising coating the upper surface of the reaction layer (12) with a hydrophilic polymer solution, and then performing drying treatment to obtain the migration layer (13 ). 10. The method according to claim 9, wherein the hydrophilic polymer solution is an aqueous solution of polyvinyl alcohol, and its weight percent concentration is 5-20%.

Images